Production of short fiber silica

ABSTRACT

A coating liquid for forming porous silica coating, comprising a product of reaction between a short fiber silica and a hydrolyzate of an alkoxysilane of the formula X n Si(OR) 4-n  or a halogenated silane of the formula X n SiX′ 4-n  (in the formula, X represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or a vinyl group; R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or a vinyl group; X′ represents a chlorine atom or a bromine atom; and n is an integer of 0 to 3). A coated substrate comprising a porous silica coating film formed from the above coating liquid for forming porous silica coating. A short fiber silica having an average diameter (D) of 10 to 30 nm, a length (L) of 30 to 100 nm and an aspect ratio (L/D) of 3 to 10. The above coating liquid for forming porous silica coating enables forming an insulating film which is excellent in adherence to a substrate surface, mechanical strength, chemical resistance and crack resistance and enables flattening irregularities of a substrate surface to a high degree. The coating film of the coated substrate has the above excellent properties.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. Ser. No. 09/130,043 filed Aug.6, 1998 now U.S. Pat. No. 6,083,314.

FIELD OF THE INVENTION

The present invention relates to a coating liquid for the formation ofporous silica coating, which enables forming an insulating film having avoid content of as large as at least 30% and having excellent adherenceto a substrate surface excellent, mechanical strength, chemicalresistance (e.g., alkali resistance) and crack resistance and whichenables the flattening of irregularities of a substrate surface to ahigh degree. Further, the present invention relates to a substrateprovided with the above porous silica coating, a short fiber silica anda process for producing such a silica.

BACKGROUND OF THE INVENTION

The silica coating is used in the following fields.

(1) Semiconductor Device:

In semiconductor devices, an insulating coating is provided, forinsulation, between a semiconductor substrate and a metal wiring layersuch as an aluminum wiring layer or between metal wiring layers.Further, in semiconductor devices, various elements such as a PNjunction semiconductor, a condenser element and a resistor elementsuperimposed on a semiconductor substrate are covered with an insulatingcoating in order to protect them. When, for example, a metal wiringlayer is disposed on the semiconductor substrate, the surface of thesemiconductor substrate becomes irregular due to the metal wiring layer.Formation of a further metal wiring layer or the like on the irregularsurface may cause a disconnection of wiring because of the leveldifference attributed to the irregularity. Consequently, insemiconductor devices, the silica coating is used as an insulatingcoating capable of effectively flattening the irregular surface broughtabout by the above metal wiring layer and other various elements.

(2) Liquid Crystal Display:

For example, the matrix type color liquid crystal display is fitted witha liquid crystal display cell comprising an electrode plate, a counterelectrode plate and a liquid crystal layer interposed between theelectrode plate and the counter electrode plate. The electrode comprisesa glass plate and, superimposed thereon, a picture element electrodecomposed of, for example, TFT (thin film transistor). The counterelectrode comprises a glass plate and, superimposed thereon, a colorfilter and transparent electrodes in this order.

In the liquid crystal display cell used in the liquid crystal display,the picture element electrode protrudes on the electrode plate and thecolor filter protrudes on the counter electrode plate, so that therespective surfaces of these electrode plates have level differences.The level differences of the electrode surfaces cause a cell gap to benonuniform, so that the alignment of liquid crystal material sealedinside the liquid crystal display cell tends to be disordered and thedisplayed image tends to suffer from picture disorder such as colorshade. Therefore, it was proposed to provide the silica coating on thepicture element electrode of the electrode plate and on the color filterof the counter electrode plate, thereby flattening irregular surfacesattributed to the picture element electrode and the color filter (seeJapanese Patent Laid-open Publication No. 2(1990)-242226).

(3) Photomask with Phase Shifter:

The method is known in which the silica coating is provided as a phaseshifter disposed for deviating the phase of irradiation light on aphotomask so that a high-resolution irregular pattern is formed on asubstrate by lithography, thereby enhancing the resolution of irregularpattern formed on the substrate (Nikkei Microdevice No. 71, 52 58, (5),1991).

The silica coating employed in the above fields is generally formed onthe substrate by the vapor phase growing method such as the CVD processor sputtering process or the coating method in which a coating film isformed from a coating liquid for forming silica coating. However, thevapor phase growing method such as the CVD process has drawbacks in thatworkload is heavy and large facilities are required and in that it isdifficult to flatten the irregular surface of the substrate.

By contrast, the coating method is widely performed because largefacilities are not required and because the flattening of the irregularsurface can easily be carried out.

In the formation of the silica coating according to the above coatingmethod, use is made of a coating liquid for forming silica coating whichcontains a polycondensate of a partial hydrolyzate of alkoxysilane as afilm forming component. However, the formation of the coating film fromthe above coating liquid for forming silica coating has a drawback inthat, during the stage of polycondensation of the partial hydrolyzate ofalkoxysilane, silanol groups mutually induce a dehydration reaction atsegments other than the terminals of the condensate so that thecrosslinking of the condensate is advanced. This, in the formation ofthe silica coating, leads to an intense film shrinkage stress, therebycausing a film cracking with the result that it is difficult to obtain asilica coating having excellent crack resistance.

By contrast, the coating liquid for forming silica coating whichcontains fine particles of silica was proposed (see, for example,Japanese Patent Laid-open Publication No. 5(1993)-263045). It is knownthat the formation of the silica coating from the above coating liquidimproves the crack resistance of the silica coating to a certain degree.In this coating liquid for forming silica coating, spherical silicaparticles obtained by hydrolyzing an alkoxysilane are used as the fineparticles of silica. However, unreacted alkoxy groups remain in suchfine particles of silica, so that, at the time of film formation, thealkoxy groups are oxidized so as to change to silanol groups. Thesilanol groups are likely to undergo a dehydration reaction to therebyadvance the crosslinking of the condensate with the result that thecrack resistance of the coating film is not satisfactory. A furtherproblem is that because the fine particles of silica are spherical, thebonding strength between the fine particles of silica is unsatisfactory,thereby resulting in unsatisfactory film strength.

The inventors have conducted extensive studies on the basis of the aboveviews. As a result, it has been found that

fine particles of silica prepared under specified conditions scarcelycontain unreacted alkoxy groups and are in the form of short fibers;

the silica coating film formed from the coating liquid which containsthe above short fiber silica is porous and maintains a desirable filmstrength; and

a coated substrate whose performance is superior to that of the priorart can be obtained by the use of the above coating liquid whichcontains the short fiber silica. The present invention has beencompleted on the basis of these findings.

The present invention has been made with a view toward solving the aboveproblem of the prior art. An object of the present invention is toprovide a coating liquid for forming porous silica coating, whichenables the formation of an insulating film having excellent inadherence to a substrate surface, excellent mechanical strength,chemical resistance (e.g., alkali resistance) and crack resistance andwhich enables the flattening of irregularities of a substrate surface toa high degree. Another object of the present invention is to provide asubstrate furnished with the above porous silica coating havingexcellent properties.

SUMMARY OF THE INVENTION

The coating liquid for forming porous silica coating according to thepresent invention comprises a product of reaction between:

a short fiber silica, and

a hydrolyzate of an alkoxysilane represented by the below indicatedgeneral formula [1] or a halogenated silane represented by the belowindicated general formula [2]:

X_(n)Si(OR)_(4-n)  [1],

X_(n)SiX′_(4-n)  [2],

wherein X represents a hydrogen atom, a fluorine atom, an alkyl grouphaving 1 to 8 carbon atoms, an aryl group or a vinyl group; R representsa hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an arylgroup or a vinyl group; X′ represents a chlorine atom or a bromine atom;and n is an integer of 0 to 3.

The above short fiber silica is preferably one obtained by hydrolyzingat least one alkoxysilane represented by the above general formula (11and, thereafter, subjecting the hydrolyzate to a hydrothermal treatmentat 250° C. or higher temperature.

The coated substrate of the present invention comprises a porous silicacoating film formed from the above coating liquid for forming poroussilica coating. The short fiber silica of the present invention has anaverage diameter (D) of 10 to 30 nm, a length (L) of 30 to 100 nm and anaspect ratio (L/D) of 3 to 10.

This short fiber silica can be produced by a process comprising thesteps of:

adding a catalyst such as ammonia to a solution of a mixture of water,an organic solvent and at least one alkoxysilane represented by theabove general formula [1] to thereby conduct a hydrolysis of thealkoxysilane so that fine particles of silica having a particle size of10 to 30 nm are produced;

removing any unreacted alkoxysilane, the organic solvent and thecatalyst from the thus obtained reaction mixture solution to therebyobtain a water dispersion of fine particles of silica;

regulating so that the water dispersion has a fine silica particle solidcontent of 0.1 to 5% by weight and a catalyst concentration of 50 to 400ppm in the term of ammonia; and

subjecting the water dispersion to a hydrothermal treatment at 250° C.or higher temperature.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is an electron micrograph of a short fiber silica; and

FIG. 2 is an electron micrograph of fine particles of silica.

DETAILED DESCRIPTION OF THE INVENTION

The short fiber silica, coating liquid for forming porous silica coatingand coated substrate according to the present invention will bedescribed in detail below.

[Short Fiber Silica]

The short fiber silica of the present invention has an average diameter(D) of 10 to 30 nm, preferably, 10 to 20 nm, a length (L) of 30 to 100nm, preferably, 30 to 60 nm and an aspect ratio (L/D) of 3 to 10,preferably, 3 to 5. When the length is smaller than 30 nm, the coatingfilm is not porous. On the other hand, when the length is greater than100 nm, defects are likely to occur at the time of fine working during aphotolithography step.

The above short fiber silica can be obtained by: hydrolyzing at leastone alkoxysilane represented by the general formula:

X_(n)Si(OR)_(4-n)  [1]

wherein X represents a hydrogen atom, a fluorine atom, an alkyl grouphaving 1 to 8 carbon atoms, an aryl group or a vinyl group; R representsa hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an arylgroup or a vinyl group; and n is an integer of 0 to 3, and, thereafter,

subjecting the hydrolyzate to a hydrothermal treatment at 250° C. orhigher temperature.

Examples of the alkoxysilanes represented by the general formula [1]include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane,tetrabutoxysilane, tetraoctylsilane, methyltrimethoxysilane,methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane,octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, trimethoxysilane,triethoxysilane, triisopropoxysilane, fluorotrimethoxysilane,fluorotriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,diethyldimethoxysilane, diethyldiethoxysilane, dimethoxysilane,diethoxysilane, difluorodimethoxysilane, difluorodiethoxysilane,trifluoromethyltrimethoxysilane and trifluoromethyltriethoxysilane.

The hydrolysis of these alkoxysilanes is conducted in the presence ofwater, an organic solvent and a catalyst.

Examples of suitable organic solvents include alcohols, ketones, ethersand esters. Specifically, use can be made of alcohols such as methanol,ethanol, propanol and butanol, ketones such as methyl ethyl ketone andmethyl isobutyl ketone, glycol ethers such as methyl cellosolve, ethylcellosolve and propylene glycol monopropyl ether, glycols such asethylene glycol, propylene glycol and hexylene glycol and esters such asmethyl acetate, ethyl acetate, methyl lactate and ethyl lactate.

As the catalyst, use can be made of basic compounds such as ammonia,amines, alkali metal hydrides, quaternary ammonium compounds and aminecoupling agents.

The amount of water required for the hydrolysis of the abovealkoxysilane is preferably 0.5 to 50 mol, still preferably, 1 to 25 molper mol of the group Si—OR as a constituent of the alkoxysilane. Thecatalyst is preferably added in an amount of 0.01 to 1 mol, stillpreferably, 0.05 to 0.8 mol per mol of the alkoxysilane. The hydrolysisof the above alkoxysilane is generally conducted at temperatures lowerthan the boiling point of the employed solvent, preferably, attemperatures of 5 to 10° C. lower than the boiling point underatmospheric pressure. However, when a heat resistant, pressure resistantvessel such as an autoclave is used, the hydrolysis temperature can behigher than the above.

When the hydrolysis is conducted under the above conditions, thepolycondensation of the alkoxysilane is developed three-dimensionally,so that silica particles having a particle size of 10 to 30 nm areproduced. Short fiber silica can be obtained by subjecting the producedfine particles of silica to a hydrothermal treatment at 250° C. orabove, preferably, 270° C. or above. This short fiber silica can beproduced by, for example, the following process.

(1) First, a catalyst is added to a solution of a mixture of water, anorganic solvent and at least one alkoxysilane represented by the abovegeneral formula [1] to thereby conduct a hydrolysis of the alkoxysilaneso that fine particles of silica having a particle size of 10 to 30 nmare produced.

(2) Subsequently, any unreacted alkoxysilane, the organic solvent andthe catalyst are removed from the thus obtained reaction mixturesolution to thereby obtain a water dispersion of fine particles ofsilica. The removal of unreacted alkoxides, the organic solvent and thecatalyst can be performed by the use of, for example, an ultrafiltrationmembrane.

(3) According to necessity, water is added to the obtained waterdispersion so that the solid content (fine particles of silica) thereofis regulated to 0.1 to 5% by weight, preferably, 0.5 to 2% by weight.Also, according to necessity, an additional alkali such as ammonia isadded to the obtained water dispersion so that the catalystconcentration is regulated to 50 to 400 ppm, preferably, 50 to 200 ppmand, still preferably, 50 to 100 ppm in the term of ammonia. In thisconnection, when ammonia is used as the catalyst for alkoxysilanehydrolysis and when the amount of ammonia remaining in the dispersionfalls in the above range, it is not necessary to add further ammonia.

(4) The thus obtained water dispersion is subjected to a hydrothermaltreatment at 250° C. or higher temperature, preferably, 270° C. orhigher temperature.

The hydrothermal treatment is performed in a heat resistant, pressureresistant vessel such as an autoclave,

The short fiber silica having a particle size of 10 to 30 nm can beobtained by this hydrothermal treatment which would give thetwo-dimensional growth of the above fine particles of silica.

The morphological change of silica particles by the hydrothermaltreatment can be controlled by the above ammonia concentration andtreatment temperature. For example, when the amount of ammonia is toosmall, the obtained short fiber silica lacks stability and may be likelyto suffer from aggregation. On the other hand, when the amount ofammonia is too large, it may happen that the short fiber silica cannotbe obtained. After the hydrothermal treatment, the dispersion of shortfiber silica can be deionized by bringing it into contact with an ionexchange resin. This deionization enables the enhancement of thereactivity with the silane compound as described below.

The thus obtained short fiber silica scarcely contains residual alkoxygroups and is a porous material with low density.

[Coating Liquid for Forming Porous Silica Coating]

The coating liquid for forming porous silica coating according to thepresent invention comprises a product of reaction between:

a short fiber silica, and

a hydrolyzate of an alkoxysilane represented by the general formula [1]or a halogenated silane represented by the general formula [2].

The short fiber silica is as mentioned above.

Hydrolyzate of Alkoxysilane or Halogenated Silane

In the present invention, use is made of a hydrolyzate of analkoxysilane represented by the below indicated general formula [1] or ahalogenated silane represented by the below indicated general formula[2]:

X _(n) Si(OR)_(4-n)  [1],

X _(n) SiX′_(4-n)  [2],

wherein X represents a hydrogen atom, a fluorine atom, an alkyl grouphaving 1 to 8 carbon atoms, an aryl group or a vinyl group; R representsa hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an arylgroup or a vinyl group; X′ represents a chlorine atom or a bromine atom;and n is an integer of 0 to 3.

The alkoxysilane represented by the general formula [1] is as mentionedabove.

The halogenated silane represented by the general formula [2] is, forexample, trichlorosilane, tribromosilane, dichlorosilane,fluorotrichlorosilane or fluorotribromosilane.

The above hydrolyzate of alkoxysilane or halogenated silane is obtainedby subjecting the alkoxysilane or halogenated silane to hydrolysis andpolycondensation in the presence of water, an organic solvent and acatalyst.

The organic solvent used in the hydrolysis is as mentioned above.

As the catalyst, use can be made of not only those mentionedhereinbefore but also an inorganic acid such as hydrochloric acid,nitric acid or sulfuric acid, an organic acid such as acetic acid,oxalic acid or toluenesulfonic acid, or a compound exhibiting acidity ina water solution such as metallic soap.

The amount of water required for this hydrolysis is preferably 0.1 to 5mol, still preferably, 0.1 to 2 mol per mol of the group Si—OR as aconstituent of the alkoxysilane or the group Si—X′ as a constituent ofthe halogenated silane.

The catalyst is preferably added in an amount of 0.001 to 1 mol per molof the alkoxysilane or halogenated silane.

It is preferred that the number average molecular weight of thehydrolyzate obtained by the hydrolysis conducted under the aboveconditions ranges from 1000 to 50,000, especially, 2000 to 20,000(molecular weight in terms of polystyrene).

The use of this hydrolyzate suppresses the aggregation of fine particlesof silica and a gelation and enables obtaining a stable coating liquid.

Product of Reaction Between Short Fiber Silica and Above-mentionedHydrolyzate

It is presumed that, in this reaction product, the above hydrolyzate isbonded to at least part of the surface of the short fiber silica.

This reaction product can be obtained by first mixing the abovedispersion of short fiber silica with the above hydrolyzate and thenheating the mixture at about 100° C. or below, preferably, 80° C. orbelow for 0.5 to 20 hr, preferably, 0.5 to 10 hr.

The mixing and reaction of the short fiber silica with the hydrolyzateof alkoxysilane or halogenated silane is preferably conducted in aweight ratio of [weight of short fiber silica (A)]/[weight ofhydrolyzate (B)] ranging from 0.1 to 20, still preferably, 1 to 10.

When the weight of the short fiber silica (A) is too large, the obtainedsilica coating becomes a porous material containing a large proportionof intergranular voids of short fiber silica, so that, although the voidcontent is large, the adherence to a substrate surface, mechanicalstrength and chemical resistance (e.g., alkali resistance) are poor andit is probable that the crack resistance and adherend surface flatteningcapability will be deteriorated. On the other hand, when the weight ofthe hydrolyzate (B) is too large, the obtained silica coating has itsintergranular voids of short fiber silica filled with the hydrolyzate(B), so that it is probable for the increase of void content to beinfeasible.

With respect to the reaction between the short fiber silica and thehydrolyzate, it is presumed that the growth of short fiber silica or theformation of new silica particles would not occur and that a surfacereaction between the short fiber silica and the hydrolyzate would occuron the surface of the short fiber silica.

It is preferred that this reaction product be contained in the coatingliquid for forming porous silica coating in an amount of 5 to 40% byweight, especially, 10 to 3.0% by weight in terms of solid content (inthe term of SiO₂).

When the silica coating is formed from the coating liquid containing theabove reaction product, not only does the coating film become porous dueto the intergranular voids of short fiber silica but also thehydrolyzate bonded to the surface exerts the effect of preventing there-adsorption of water onto the intergranular voids of the coating film.Further, the silica particles are in the form of fibers, so that thefilm strength is maintained. Therefore, a stable porous silica coatingwith excellent flattening performance can be formed.

No peak ascribed to the group OH is observed in the analysis of an FT-IRspectrum of the silica coating film obtained by applying the coatingliquid containing the above reaction product onto a substrate, heatingat 400° C. in an oxygen containing gas atmosphere (for example, nitrogengas that contains 1000 ppm of oxygen) and allowing the fired coatedsubstrate at ordinary room temperature for one week.

[Coated Substrate]

The coated substrate of the present invention comprises a porous silicacoating film formed from the above coating liquid.

This coated substrate is obtained by applying the above coating liquidto a surface of any of various substrates and heating.

The application of the coating liquid can be conducted by variousmethods such as the spraying method, spin coating method, dip coatingmethod, roll coating method and transfer printing method. The heating ofcoating liquid is conducted at 300 to 450° C., preferably, 350 to 400°C.

The above heating may be accompanied by the curing of coating which iseffected by irradiation with ultraviolet rays or electron beams or byplasma treatment.

The coated substrate of the present invention is used in, for example,an electronic component such as a semiconductor device, a liquid crystaldisplay, a printed circuit board or LSI element having a multilayerwiring structure, a hybrid IC or an alumina substrate, a photomask witha phase shifter, or a triple layer resist.

In the semiconductor device, the porous silica coating is formed, forexample, on a silicon substrate, between wiring layers of asemiconductor device having a multilayer wiring structure, on an elementsurface or on a PN junction part.

In the liquid crystal display cell of the color liquid crystal display,the porous silica coating is formed between a TFT element and an ITOpicture element electrode layer.

In the phase shifter of the photomask with phase shifter and the triplelayer resist, the porous silica coating is constructed in anintermediate layer. Furthermore, in the above electronic components, theporous silica coating is formed as a flattening film. Although varieddepending on the substrate to be coated and the object, for example, thethickness of the porous silica coating formed in the above manner rangesfrom about 100 to 250 nm in the formation on a silicon substrate of asemiconductor device and ranges from 300 to 500 nm in the formationbetween wiring layers of a multilayer wiring.

The coating liquid for forming porous silica coating according to thepresent invention enables the formation of a porous insulating filmwhich has excellent adherence to a substrate surface, excellentmechanical strength, chemical resistance (e.g., alkali resistance) andcrack resistance and further enables the flattening of irregularities ofa substrate surface to a high degree.

The coated substrate of the present invention is furnished with a porousinsulating film which has excellent adherence to a substrate surface,excellent mechanical strength, chemical resistance (e.g., alkaliresistance) and crack resistance and realizes flattening ofirregularities of a substrate surface to a high degree.

EXAMPLE

The present invention will now be illustrated in greater detail withreference to the following Examples, which in no way limit the scope ofthe invention.

Production Examples

1. Preparation of Short Fiber Silica:

139.1 g of pure water was mixed with 169.9 g of methanol to therebyobtain a mixed solvent. The mixed solvent was held at 60° C., and 2982.5g of a water/methanol solution of tetraethoxysilane (Ethyl Silicate 28produced by Tama Chemicals Co., Ltd.) (532.5 g of tetraethoxysilanedissolved in 2450 g of a water/methanol (weight ratio: 2/8) mixedsolvent) and 596.4 g of 0.25% aqueous ammonia were simultaneously addedthereto over a period of 20 hr by a dropping method. After thecompletion of the addition, the mixture was aged at the same temperaturefor 3 hr. Thereafter, unreacted tetraethoxysilane, methanol and ammoniawere nearly completely removed with the use of an ultrafiltrationmembrane, and pure water was added so that the silica content wasregulated to 1% by weight. The ammonia concentration was measured bymeans of an ion electrode and found to be 83 ppm.

The mixture was subjected to a hydrothermal treatment in a 300° C.autoclave for 10 hr and, after the treatment, purified with the use ofamphoteric ion exchange resin (AG-501 produced by Bio-Rad). Thus, shortfiber silica (A) having an average diameter of 20 nm and a length ofabout 80 nm was obtained.

A transmission electron micrograph of obtained short fiber silica (A) isshown in FIG. 1.

The hydrolysis of tetraethoxysilane was carried out in the same manneras described above and the purification was performed by ultrafiltrationto thereby regulate the silica content and the ammonia concentration to1% by weight and 105 ppm, respectively. Hydrothermal treatment wasperformed in a 200° C. autoclave for 10 hr. Thus, fine particles ofsilica (B) having an average diameter of 20 nm were obtained.

A transmission electron micrograph of obtained fine particles of silica(B) is shown in FIG. 2.

2. Preparation of Hydrolyzates of Alkoxysilane and Halogenated Silane:

250 g of triethoxysilane was mixed with 750 g of methyl isobutyl ketone,and 1000 g of a 0.01% by weight aqueous hydrochloric acid solution wasadded thereto. The mixture was reacted at 50° C. for 1 hr underagitation. The reaction mixture was allowed to stand still, and an upperlayer forming methyl isobutyl ketone solution was separated, therebyobtaining hydrolyzate (C).

Trichlorosilane was hydrolyzed by the method described in JapanesePatent Publication No. 6(1994)41518, and the thus obtainedhydrogensilsesquioxane was dissolved in methyl isobutyl ketone. Thus,hydrolyzate (D) was obtained.

3. Preparation of Coating Liquid for Forming Coating Film:

Water and alcohol were distilled off from the above obtained dispersionsof short fiber silica (A) and fine particles of silica (B) by the use ofa rotary evaporator, and solvent replacement with methyl isobutyl ketonewas carried out. The thus obtained silica containing dispersions (A) and(B) and the hydrolyzates (C) and (D) were mixed together in proportionsspecified in Table 1 and heated at 50° C. for 1 hr. Thereafter, thealcohol and water produced by the heating were completely removed bymeans of a rotary evaporator, and solvent replacement with methylisobutyl ketone was carried out again. Thus, coating liquids (1) to (4)having a silica content of 20% by weight were obtained for formingcoating film. In addition, coating liquids (5) and (6) having no silicacontent were prepared.

TABLE 1 Coating Wt. ratio (silica fine liquid Silica Hydrolyzateparticles/hydrolyzate) 1) fiber silica (A) (C) 9/1 2) fiber silica (A)(D) 9/1 silica fine 3) particles (B) (C) 9/1 silica fine 4) particles(B) (D) 9/1 5) — (C) 6) — (D)

Examples 1 and 2 and Comparative Examples 1 to 4

Semiconductor Device:

Each of the coating liquids (1) to (6) as shown in Table 1 was appliedby the spin coating method to a semiconductor substrate furnished withminimum 0.25 μ rule metal wiring and dried at 250° C. for 3 min.Thereafter, heating was conducted at 400° C. for 30 min in a nitrogengas atmosphere or in a 5% oxygen containing nitrogen gas atmosphere,thereby forming silica coating films with a thickness of 500 nm.

Upper layer metal wiring was formed on the thus prepared silica coatingfilms, thereby obtaining semiconductor devices.

With respect to each of the obtained semiconductor devices, theflattening performance, strength and relative permittivity of silicacoating film were measured. The results are given in Table 2.

The flattening performance was evaluated by observing a section of thesubstrate furnished with coating film by means of an SEM electronmicroscope; the film strength was evaluated by Sebastian tester; and therelative permittivity was measured according to the mercury probemethod.

TABLE 2 Relative permittivity after N₂ Coating Flat- Film atm. after O₂contg. liquid ness strength heating N₂ atm. heating Ex.1 1) good strong2.2 3.0 Ex.2 2) good strong 2.1 2.8 Comp 3) good weak 2.3 3.1 Ex.1 Comp4) good weak 2.2 2.8 Ex.2 Comp 5) good strong 3.0 4.5 Ex.3 Comp 6) goodstrong 2.7 4.2 Ex.4

Examples 3 and 4 and Comparative Examples 5 to 8

Color Liquid Crystal Display:

Each of the coating liquids (1) to (6) as shown in Table 1 was appliedonto a glass plate furnished with TFT element and heated, therebyforming a silica coating film. Thereafter, an ITO picture elementelectrode and a polyimide alignment coating as upper layers were formedon the top thereof. The resultant plate and a counter electrode platecomprising a glass plate and, sequentially superimposed thereon, a colorfilter, a transparent electrode and a polyimide alignment coating weresecured to each other, and a liquid crystal layer was interposedtherebetween. Thus, matrix color liquid crystal displays furnished withliquid crystal display cell were obtained.

The flattening performance, presence of cracking, presence of cross-talkand display performance of silica coating film were evaluated withrespect to each of the thus obtained color liquid crystal displays. Theresults are given in Table 3.

The cracking and the presence of cross-talk were visually inspected, andthe display performance was evaluated by luminance and contrast.

TABLE 3 Coating Flat- Display liquid ness Crack Cross-talk performanceEx.3 1) good none none good Ex.4 2) good none none good Comp 3) goodnone none good Ex.5 Comp 4) good none none good Ex.6 Comp 5) good foundfound poor Ex.7 Comp 6) good found found poor Ex.8

What is claimed is:
 1. A process for producing a short fiber silica,comprising the steps of: adding a catalyst to a solution of a mixture ofwater, an inorganic solvent and at least one alkoxysilane represented bythe general formula X_(n)Si(OR)_(4-n) to thereby conduct a hydrolysis ofthe alkoxysilane so that fine particles of silica having a particle sizeof 10 to 30 nm are produced; removing any unreacted alkoxysilane, theorganic solvent in the catalyst from the thus obtained reaction mixturesolution to thereby obtain a water dispersion of fine particles ofsilica; regulating so that the water dispersion has a fine particlesolid content of 0.1 to 5% by weight and a catalyst concentration of 50to 400 ppm in the term of ammonia; subjecting the water dispersion to ahydrothermal treatment at 250° C. or higher temperature; and wherein Xrepresents a hydrogen atom, a flourine atom, an alkyl group having 1 to8 carbon atoms, an aryl group or a vinyl group; R represents a hydrogenatom, and alkyl group having 1 to 8 carbon atoms; an aryl group or avinyl group; and n is an integer of 0 to
 3. 2. The process for producinga short fiber silica as claimed in claim 1, wherein the catalyst isammonia.
 3. A short fiber silica having an average diameter (D) of 10 to30 nm, a length (L) of 30 to 100 nm and an aspect ratio (L/D) of 3 to10, which is obtainable from the process as claimed in claim 1.